Biodiesel production from Jathropha curcas l. oil using chemical or enzymatic catalysts

Doutoramento em Engenharia dos Biossistemas - Instituto Superior de Agronomia - UL

Estudo da polimerização térmica de óleos e gorduras

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2011.

Influence of the metal precursor on the catalytic behavior of Pt/Ceria catalysts in the preferential oxidation of CO in the presence of H2 (PROX)

The effect of the metal precursor (presence or absence of chlorine) on the preferential oxidation of CO in the presence of H2 over Pt/CeO2 catalysts has been studied. The catalysts are prepared using (Pt(NH3)4)(NO3)2 and H2PtCl6, as precursors, in order to ascertain the effect of the chlorine species on the chemical properties of the support and on the catalytic behavior of these systems in the PROX reaction. The results show that chloride species exert an important effect on the redox properties of the oxide support due to surface chlorination. Consequently, the chlorinated catalyst exhibits a poorer catalytic activity at low temperatures compared with the chlorine-free catalyst, and this is accompanied by a higher selectivity to CO2 even at high reaction temperatures. It is proposed that the CO oxidation mechanism follows different pathways on each catalyst.

Selective hydrogenation by novel composite supported Pd egg-shell catalysts

Two organic–inorganic mixed phase supports were prepared, comprising an alumina filler and polymers of different chemical nature. Four low loaded Pd catalysts were prepared. Good activities and selectivities were obtained during the hydrogenations of styrene, 1-heptyne and 2,3-butanedione. The catalysts were found to have excellent mechanical properties and could be used in applications needing high attrition resistance and crushing strength. In this sense, processes for fine chemicals using slurry reactors or processes for commodities using long packed beds could advantageously use them.

High performance of Cu/CeO2-Nb2O5 catalysts for preferential CO oxidation and total combustion of toluene

Copper-based catalysts supported on niobium-doped ceria have been prepared and tested in the preferential oxidation of CO in excess of H2 (PROX) and in total oxidation of toluene. Supports and catalysts have been characterized by several techniques: N2 adsorption, ICP-OES, XRF, XRD, Raman Spectroscopy, SEM, TEM, H2-TPR and XPS, and their catalytic performance has been measured in PROX, with an ideal gas mixture (CO, O2 and H2) with or without CO2 and H2O, and in total oxidation of toluene. The effects of the copper loading and the amount of niobium in the supports have been evaluated. Remarkably, the addition of niobia to the catalysts may improve the catalytic performance in total oxidation of toluene. It allows us to prepare cheaper catalysts (niobia it is far cheaper than ceria) with improved catalytic performance.

Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming

A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts’ stability when working under more severe reaction conditions.

Active oxygen by Ce–Pr mixed oxide nanoparticles outperform diesel soot combustion Pt catalysts

A Ce0.5Pr0.5O2 mixed oxide has been prepared with the highest surface area and smallest particle size ever reported (125 m2/g and 7 nm, respectively), also being the most active diesel soot combustion catalyst ever tested under realistic conditions if catalysts forming highly volatile species are ruled out. This Ce–Pr mixed oxide is even more active than a reference platinum-based commercial catalyst. This study provides an example of the efficient participation of oxygen species released by a ceria catalyst in a heterogeneous catalysis reaction where both the catalyst and one of the reactants (soot) are solids. It has been concluded that both the ceria-based catalyst composition (nature and amount of dopant) and the particle size play key roles in the combustion of soot through the active oxygen-based mechanism. The composition determines the production of active oxygen and the particle size the transfer of such active oxygen species from catalyst to soot.

Opportunities for ceria-based mixed oxides versus commercial platinum-based catalysts in the soot combustion reaction. Mechanistic implications

The aim of this paper is to study the activities of ceria–zirconia and copper/ceria–zirconia catalysts, comparing with a commercial platinum/alumina catalyst, for soot combustion reaction under different gas atmospheres and loose contact mode (simulating diesel exhaust conditions), in order to analyse the kinetics and to deduce mechanistic implications. Activity tests were performed under isothermal and TPR conditions. The NO oxidation to NO2 was studied as well. It was checked that mass transfer limitations were not influencing the rate measurements. Global activation energies for the catalysed and non-catalysed soot combustion were calculated and properly discussed. The results reveal that ceria-based catalysts greatly enhance their activities under NOx/O2 between 425 °C and 450 °C, due to the “active oxygen”-assisted soot combustion. Remarkably, copper/ceria–zirconia shows a slightly higher soot combustion rate than the Pt-based catalyst (under NOx/O2, at 450 °C).

Platinum–tin/carbon catalysts for ethanol oxidation: Influence of Sn content on the electroactivity and structural characteristics

Carbon-supported Pt–Sn catalysts commonly contain Pt–Sn alloy and/or Pt–Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt–Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Ptx–Sny/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt1–Sn1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt–Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt2–Sn1/C and Pt3–Sn1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt–Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Ptx–Sny/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method.

Dimeric assemblies of lanthanide-stabilised dilacunary Keggin tungstogermanates: A new class of catalysts for the selective oxidation of aniline

In this work we demonstrate the efficiency of some dimeric [Ln4(H2O)6(β-GeW10O38)2]12− anions composed of lanthanide-stabilised dilacunary Keggin tungstogermanate fragments (ββ-Ln4, Ln = Dy, Ho, Er, Tm) as heterogeneous catalysts for the organic phase oxidation of aniline with hydrogen peroxide. The results obtained evidence total conversion of aniline at room temperature, as well as full selectivity towards nitrosobenzene, and the catalysts are able to retain both their activity and selectivity after several runs. Peroxopolyoxometalate intermediaries have been identified as the catalytically active species during the aniline-to-nitrosobenzene oxidation process.

In situ characterization of porous VPO catalysts with fibrous structure: Identifying the redox behavior and the stability of active sites

Two VPO materials with fibrillar morphology have been prepared by the aid of electrospinning technique. One is a VPO carbon-supported material (VCF200) with fibrous morphology and very high surface area that is stable under oxidizing conditions up to 350C. The other material is a bulk mixed VPO oxide (VPO500) with fibrous structure obtained after optimizing the calcination of the carbon support in VCF200. Despite it is a bulk oxide material, this material exhibits a high surface area (> 60 m2/g). The redox behavior of both samples was monitored by in situ Raman spectroscopy under oxidation/reduction cycles. For the dehydrated supported sample (VCF200), the pyrophosphate phase (VO)2P2O7 (Raman ~930 cm-1) is detected, which has been described as the active phase (see Figure (a) below). This phase is quite stable since it does not disappear upon subsequent oxidation/reduction cycles. Under reduction conditions at 125C, in consecutive cycles, additional Raman bands appear at ~1090 cm-1 that are characteristic of the αII-VOPO4 phase. On the other hand, the bulk phases show a reversible behavior under redox cycles (Figure (b)). Under reducing conditions, a Raman band appears at ~980 cm-1 (β-VPO phase), whereas under oxidation conditions some segregation to VOx oxides occurs. Nevertheless, this segregation is reversible and the β-VPO phase forms again under reducing conditions. Thus, these results demonstrate that the active VPO phases of these fibrous catalysts are quite stable, and that their structure is reversible under several redox cycles, which make them suitable as oxidation catalysts.

Mesoporous mixed Nb2O5-ZrO2 catalysts for dehydration of glucose into 5-hydroxymethylfurfural

Biomass is the world’s most important renewable carbon source, whose major component, carbohydrates, can be valorized by transformation into biofuels and high value-added chemicals. Among the latter, 5-hydroxymethylfurfural (HMF), obtained by C6 carbohydrates dehydration, is a versatile and key intermediate for the production of a large spectrum of biobased chemicals. Different catalytic systems have been evaluated for HMF production, mostly based on heterogeneous catalysis as alternative to the use of conventional mineral acids [1]. Moreover, niobium oxide has shown interesting properties as acid catalyst for dehydration of sugars [2-3]. On the other hand, the high surface area and large pore size of mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous mixed Nb2O5-ZrO2 in a biphasic water–Methyl Isobutyl Ketone (MIBK) solvent system to avoid the HMF degradation. Different experimental parameters, such as reaction temperature and time, as well as the addition of CaCl2 have been studied in order to maximize the HMF yield.N2 adsorption-desorption isotherms have corroborated the mesostructured character of catalysts, being all isotherms of Type IV according to the IUPAC classification. BET surface area decreases for catalysts with higher Zr content (Table 1). Likewise, pore volume and average pore diameter values diminish after Zr incorporation. Concerning the acid properties, a clear correlation between Nb and acidity can be observed, in such a way that total acidity, as deduced from NH3-TPD, decreases when the Zr content rises, and consequently the amount of Nb is reduced.These mesoporous Nb-Zr catalysts have been tested in the dehydration of glucose to HMF at 175 ºC under batch operation in aqueous solution, using MIBK as co-solvent. It can be observed that both glucose conversion and HMF yield increase with the Nb content, being maximum (90% and 36%, respectively) after 90 minutes for Nb2O5. This trend changes when CaCl2 is added to the reaction medium, improving the catalytic performance of mixed oxides and ZrO2, but Nb2O5 maintains similar results than without salt addition. This could be justified by the interaction between CaCl2 and Lewis acid sites, since zirconium oxide possesses a higher amount of this acid sites type.

Fouling in emulsion polymerization reactors

160 p.

Niobic acid nanoparticle catalysts for the aqueous phase transformation of glucose and fructose to 5-hydroxymethylfurfural

A family of bulk and SBA-15 supported peroxo niobic acid sols were prepared by peptisation of niobic acid precipitates with H2O2 as heterogeneous catalysts for aqueous phase glucose and fructose conversion to 5-hydroxymethylfurfural (5-HMF). Niobic acid nanoparticles possess a high density of Brønsted and Lewis acid sites, conferring good activity towards glucose and fructose conversion, albeit with modest 5-HMF yields under mild reaction conditions (100 °C). Thermally-induced niobia crystallisation suppresses solid acidity and activity. Nanoparticulate niobic acid dispersed over SBA-15 exhibits pure Brønsted acidity and an enhanced Turnover Frequency for fructose dehydration.

Octyl co-grafted PrSO3H/SBA-15:tunable hydrophobic solid acid catalysts for acetic acid esterification

Propylsulfonic acid (PrSO3H) derivatised solid acid catalysts have been prepared by post modification of mesoporous SBA-15 silica with mercaptopropyltrimethoxysilane (MPTMS), with the impact of co-derivatisation with octyltrimethoxysilane (OTMS) groups to impart hydrophobicity to the catalyst investigated. Turn over frequencies (TOF) for acetic acid esterification with methanol increase with PrSO3H surface coverage across both families suggesting a cooperative effect of adjacent acid sites at high acid site densities. Esterification activity is further promoted upon co-functionalisation with hydrophobic octyl chains, with inverse gas chromatography (iGC) measurements indicating increased activity correlates with decreased surface polarity or increased hydrophobicity.